The aim of this study was to assess the prevalence of dental pain and associated socio-demographic and behavioral factors in Brazilian adolescents, using data from the National School-Based Health Survey (PeNSE), Brazil, 2009. The survey was conducted by the Brazilian Institute of Geography and Statistics (IBGE) and Ministry of Health in students 11 to 17 years of age or older in the 27 State capitals, using a self-administered questionnaire. Analyses included Poisson regression following a hierarchical approach. Prevalence of dental pain in the sample (n = 54,985) in the previous six months was 17.8% (95%CI: 17.5-18.1). Higher prevalence was associated with female gender, age 14 years and over, racial self-identification as black, brown, or indigenous, enrollment in public schools, lower maternal schooling, not living with the mother, history of smoking or drinking, less frequent toothbrushing, and heavy consumption of sweets and soft drinks. Dental pain was thus associated with socio-demographic factors and health-related behaviors.